JP5160900B2 - Mounting the film on a transparent substrate - Google Patents

Description

  The present invention relates to substrates, especially transparent substrates, which are occasionally or permanently at temperatures below 0 ° C.

  Frost protection, hydrophobicity, hydrophilicity, anti-fouling / (photocatalytic) self-cleaning, reflection of light or heat radiation, at least partial coloring, electrical conduction / heating, semi-permeability that allows transparency to be protected Various functionalities such as conductivity, antistatic, electroluminescent, etc. can be imparted to such a substrate.

  Some of these functions may be combined on the substrate, for example in the form of a coating. In this case, the method for forming the coating provides the desired adhesion and mechanical strength and the lowest possible scratchability, especially if the substrate is transparent, or the ability to self-repair scratches in the coating. Adapted to guarantee. Of course, the coating will regenerate if necessary.

  On the other hand, one or more functions may be provided by an adhesive film having the advantage of being easily replaced by the same film or a film having a different function.

Obviously in such cases, it is attempted to obtain a complete adhesion quality of the film on the substrate , in particular by avoiding trapping air bubbles between the substrate and the film . To do this, one method is sufficient to allow all bubbles to be expelled by applying pressure to the film, for example using a scraper from its central part to its outer periphery. It may comprise interposing an amount of liquid, in particular water as a mixture with the surfactant.

  However, this method does not give satisfactory results with substrates that are occasionally or permanently at temperatures below 0 ° C. In fact, after being assembled, the portion of the liquid that remains between the substrate and the film can be crystallized by the formation of frost. Thus, when a functional adhesive film is applied inside a transparent refrigerated cabinet door at a temperature that can be, for example, between -28 and 0 ° C., frost is generated so that it can no longer be seen through the door To do. Depending on the permeability of the film and the relative dryness of the refrigerated atmosphere, it is likely that the frost will disappear at least 4 days to a week or more after it has formed. Such inconvenience hinders its use as a vertical door in refrigerated cabinets in superstores, and it is essential in the hypermarket and supermarket areas to maintain full transparency, even for customers or for restocking Permanent frost with the frequency of opening and closing.

Accordingly, it is an object of the present invention to provide a flexible film assembly to a substrate that guarantees complete inter-side between the substrate and film, and in particular a method free of trapped bubbles and frost formation. .

For this purpose, one subject of the present invention is a method for bonding the flexible film containing a sufficient amount of liquid to the substrate between the film and the substrate, the film using a scraper base After being applied to the foam, the bubbles between the film and the substrate are not trapped, occasionally or permanently below 0 ° C, particularly high -5 ° C and especially high -10 ° C, and also at least -25 ° C It is characterized by a liquid that does not freeze at the substrate temperature.

  Advantageously, the substrate is removed of all particles bound to the substrate, cleaned and dried before interposing a sufficient amount of liquid between the film and the substrate.

  Preferably, the side of the flexible film that is bonded to the substrate is wet with the sufficient amount of liquid. Any suitable technique for fixing liquids such as flow coating, spray coating or the like may be used. On the other hand, neither wetting the side of the substrate to be bonded with the film with the sufficient amount of liquid nor wetting both the side of the film and the side of the substrate is excluded.

In accordance with another preferred feature of the method of the present invention, the side of the flexible film that is adhered to the substrate includes an adhesive layer that is optionally provided with a protective film that is removed prior to adhesion to the substrate.
Alternatively, the adhesive may be incorporated into a liquid that is interposed between the film and the substrate.

The adhesive may be selected from:
Hot melt adhesive: heat that is heated to obtain a liquid with the appropriate viscosity to be applied and cooled to obtain a solid (polyethylene, ethylene / vinyl acetate copolymer, polyamide, polyester, etc.) Plastic polymers;
Adhesives in aqueous or organic solutions or dispersions in which the solvent is evaporated to obtain a solid after deposition:
In aqueous solution: natural products such as phenolic adhesives, polyvinyl methyl ether, polyvinyl alcohol, dextrin, casein, blood-based glue (serum globulin and albumin), and fish glue (derived from collagen);
In organic solution: natural rubber, acrylic, polyurethane, polyamide, polyvinyl acetal, phenoxy; and in dispersion: polyurethane, epoxy, silicone, some elastomers (nitrile rubber, etc.);
Ready-to-use adhesive in film form:
Epoxy, phenolic, nitrile rubber, polyamide, polyvinyl butyral, polyvinyl chloride, ethylene / carboxylic acid copolymer;
Adhesive with in situ polymerization reaction: cyanoacrylate, some reactive acrylics;
Pressure-sensitive adhesive: does not change the physical state before and after application, remains permanently deformable and has some tack characteristics (tack) at room temperature:
Tackified elastomer (natural rubber latex), ethylene / vinyl acetate copolymer, thermoplastic elastomer (polyurethane, etc.) / Styrene diene (styrene butadiene styrene, styrene isoprene styrene) block copolymer, polyalkyl acrylate, silicone;
Elastomers: natural rubber, styrene / butadiene rubber, polychloroprene, neoprene, nitrile rubber, butyl rubber; and inorganic adhesives: silicates that are soluble in various silica / alkali metal ratios.

According to a preferred embodiment of the method of the invention:
The opposite side of the flexible film that is adhered to the substrate is wetted with an effective amount of liquid so that the scraper can easily slide over the film during the operation of applying the film to the substrate;
The opposite side of the flexible film that is adhered to the substrate is provided with a protective film that is removed after the flexible film is adhered to the substrate; this protective film is provided with a scraper offset as indicated above. Can be particularly moistened to facilitate; and
Liquid interposed between the film and the substrate, the effective amount of soluble liquid, salts, particularly KC1, NaCl or Ru lowers the crystallization temperature of such equivalent antifreeze compounds and / or alcohols, and // A suitable hydrophilic polymer, copolymer, prepolymer or oligomer, optionally in water, and optionally one or more surfactants.
Ethanol and isopropanol are used in particular as alcohols.

The hydrophilic polymers, copolymers, prepolymers or oligomers that make up the intervening liquid are poly (n-vinyl-2-pyrrolidone) or poly (1-vinylpyrrolidone) type polyvinylpyrrolidone, poly (n-vinyl-2- pyridine) type, port Li (n- vinyl-3-pyridine) type or port Li (n- vinyl-4-pyridine) type polyvinylpyridine, poly (2-hydroxyethyl acrylate) type polyacrylate, poly (N ' , N-hydroxyacrylamide) type polyacrylamide, polyvinyl acetate, polyacrylonitrile, polyvinyl alcohol, polyacrolein, polyethylene glycol, polypropylene glycol and polyoxyethylene. In particular, the copolymers are based on at least one monomer that forms these polymers.

  Surfactants include linear, branched or unsaturated aliphatic chains or aromatic or alkylaromatic chains, and fat-soluble moieties Y that may be ionic or nonionic hydrophilic heads Compounds.

Examples of these are:
Anionic _{^{surfactants: Y-CO 2 - M +}} ; Y-OSO 3 - M +; Y-SO 3 - M +;
Dodecylbenzene sulfonate; alkyl sulfonate;
Sulfonated fatty acids and fatty acid esters; and alkylaryl sulfonates;
Cationic _{^{surfactants: Y- (R) n NH +}} (4-n), X -; Y-R 4 N +, X -; alkyltrimethylammonium;
Alkylbenzyldimethylammonium; imidazolinium salt; and amine salt;
Zwitterionic surfactant: YN ⁺ . . . CO ₂ ⁻ ;
Y-N ⁺ . . . SO ₃ ⁻ ; betaine; sulfobetaine; and imidazolium salts; and nonionic surfactants: Y—OR; Y—OH; Y—CO ₂ R; Y—CONHR;
_{Y- (CH 2 -CH 2 -O)} n; polyols; alcohol; acids, esters, and polyethoxylated fatty alcohols.

Another subject of the present invention is formed by a substrate and a flexible film adhered to each other, obtained in the absence of entrapped bubbles, with a sufficient amount of liquid intervening , 0 ° C. or higher , preferably 10 From air having a temperature of from -35 ° C. , in particular from 15 ° C. to 30 ° C. and in particular from 23 ° C. to 27 ° C. and a residual humidity of at least 25%, substrates and films are less than 0 ° C. It is characterized in that there is no frost when it is transferred to the atmosphere, which will have a temperature of 10 ° C.

  According to one preferred feature, the substrate and the flexible film form a transparent assembly. Base material is plastic such as glass or polycarbonate, polypropylene, polymethyl methacrylate, ethylene / vinyl acetate copolymer, polyethylene terephthalate, polybutylene terephthalate, polyurethane, polyvinyl butyral, etc., cycloolefin such as ethylene / norbornene or ethylene / cyclopentadiene Copolymers, polycarbonate / polyester copolymers, and similar ionomer resins, such as ethylene / (meth or acrylate) copolymers neutralized with polyamines, alone or in admixture.

According to other advantageous features of the substrate and flexible film of the present invention:
The film is an anti-frost film and / or is hydrophobic and / or hydrophilic and / or (photocatalytic) anti-fouling / self-cleaning and / or reflects light or heat radiation and is sunbeam A protective film, a low-emissivity film , and / or at least partially colored and / or electrically conductive / heated and / or semiconductive and / or antistatic and / or even electroluminescent is there;
Film, respectively, higher, -10 ° C., Ri temperature der of -15 ° C. and -20 ° C., and, 0 ° C. or higher, preferably 10 ° C. to 35 ° C., in particular 15 ° C. to 30 ° C. and in particular 23 ° C. ~ If placed in an atmosphere with a temperature of 27 ° C. and a residual humidity of at least 25% and frost does not form for at least 12 seconds, preferably at least 1 minute, in particular at least 2 minutes, at least 3 minutes , An awning film ;
Film is polyamide, polyester, polyolefin such as polyethylene or polypropylene, cellulose, polystyrene, ethylene / vinyl acetate copolymer, polyvinyl alcohol, polyvinyl chloride, polyethylene terephthalate, polymethyl methacrylate, polycarbonate, polyvinyl butyral, polyurethane, polyvinyl pyrrolidone, polyvinyl Based on a support made of pyridine, poly (2-hydroxyethyl acrylate) type polyacrylate, polyacrylamide, polyvinyl acetate, polyacrylonitrile, polyacrolein, polyethylene glycol, polyoxyethylene; at least one polymer as described above Or a copolymer or mixture based on
The film is an anti-frost film by containing antifreeze compounds that lower the crystallization temperature and, optionally, having hydrophobic characteristics on its surface portion. It is possible to use the same antifreeze compounds as described above as the intervening liquid. However, the frost protection of the film can improve the mechanical strength of the layer incorporating the antifreeze compound , especially when the layer incorporating the antifreeze compound is likely to be subjected to mechanical contact or cleaning from time to time. Functional durability is required. For this purpose, the antifreeze compound is cross-linked and / or mixed with at least one compound with physical interaction and / or in a solid, for example mineral or mixed matrix, ORMOCER (organically It may be dispersed in a mixing matrix that is of the (modified ceramic) type.

  The term “physical interaction” is understood herein to mean a hydrogen bond, a van der Waals type of polar interaction, or a hydrophobic interaction that can produce mechanical reinforcement comparable to a bridge. Is done.

  The frost protection function may be incorporated into the film itself or a coating formed on a support for the film.

Another subject of the present invention is an optional substrate in which a substrate and a flexible film as described above, and also the substrate and the flexible film are connected via an intermediate adhesive layer, or a gas filled cavity. Grazing including other transparent sheets. The flexible film advantageously forms the outer surface of the functional glazing in this way.

Glazing consists in particular of monolithic, laminated, insulating, vacuum glazing .
Such insulating glazings have, for example, two or three sheets of monolithic or laminated glass separated in pairs by gas filled cavities. Its advantage is that the refrigerated cabinet can be thermally insulating to the outside air (such as a store).

This thermal insulation may be obtained by vacuum glazing comprising monolithic or laminated glass of at least two sheets separated by a gas-filled cavity, either at vacuum or at a lower pressure. These two sheets may be combined with a third glass separated by a gas filled cavity that may be at lower pressure or not lower pressure.

  Such a structure may include one or more low emissivity layers that reflect the heat radiated by the outer surface of the refrigerated cabinet.

According to one advantageous feature of this glazing, the barrier over, that is, the elements of all the hands, whereby monolithic or various configurations sheet of laminated glass, are held together at intervals in pairs, the The thermal conductivity is at most 1.46 W / mK.

Ultimately, one subject of the present invention is the use of such glazing :
As a door of a refrigerated cabinet;
Ken creation, street furniture or poster panel, for elements of a refrigerated cabinet other than the door, such as traffic mirror and shelving;
For ground transport vehicles , airborne or water transport vehicles (windshields, side windows, rear windows, roof parts, rearview mirrors, headlights); and
For visual elements (glasses, helmet visor).

The present invention is particularly beneficial for products that are at least occasionally exposed to temperatures below 0 ° C. and has advantages over previous applications in exterior applications in harsh climatic conditions.

  The invention will be better understood in view of the following examples.

The first example of WO 00/71481 was repeated with the following exceptions:
Instead of insulating vacuum glazing , triple insulating glazing was used; and the polycarbonate film was provided with an adhesive layer oriented towards the insulating glazing to the film with the liquid intervention specified below.

  The polycarbonate film on the opposite side of the adhesive layer was coated with an adsorptive anti-frost layer forming a three-dimensional polymer network based on polyvinylpyrrolidone and polyurethane. The thickness of the frost protection layer was 14.5 μm.

  Tests were conducted on a door installed on the refrigerated cabinet and a temperature of -25.5 ° C was maintained on the inside. The temperature measured inside the door was −22 ° C. The cabinet was placed in an atmosphere with a temperature of 25 ° C. and a residual humidity of 60%.

The test was conducted as follows.
To avoid frost formation on the glass, the cabinet door was opened for 10 minutes before the film was adapted.

  The inside of the door was moistened using a sprayer filled with a cleaning composition (soap water).

  To remove all particles on the glass, the glass was rubbed with a scraper and then with a rubber squeegee to remove the water. There was no longer any frost on the door. The edges were wiped with a cloth as needed.

  The protective film was removed from the polycarbonate film adhesive and the liquid shown in the table below was sprayed onto the adhesive.

The adhesive side of the film was applied to the glass.
The other side of the film was wetted by spraying with the same liquid as on the adhesive so that the rubber squeegee could easily slide over the film.

A rubber squeegee was used to expel the liquid between the glass and the film. Scraping was performed from the center of the glazing to the outside for complete elimination of the liquid.

  If necessary, the film was cut to leave a few millimeters gap between the door post and the film to facilitate liquid drainage.

  Repeated scraping and closed the cabinet door.

  Evaluated in the table below is the presence or absence of frost at various times after closing the door, and also the presence or absence of bubbles between the glass and the film.

Percentages are given by weight.
Mir is a detergent composition from Henkel.

Triton X is a mixture of polyethoxylated octylphenol (nonionic surfactant) sold by Union Carbide.
PEG 200 is polyethylene glycol (part number 807484) sold by Merck.

  This table demonstrates the possibility of reducing frost formation until it is prevented from forming, and thus obtained permanent frost-free.

Claims (37)

Interposing a liquid between the film and the substrate so that bubbles are not trapped between the film and the substrate after the film has been applied to the substrate using a scraper. comprising a method for adhering a frost flexible film to the substrate to form a transparent assembly, liquid, so as not to freeze at substrate temperatures below 0 ° C., forming a dissolved solution A process comprising an antifreeze compound and / or an alcohol and / or a hydrophilic polymer, copolymer, prepolymer or oligomer that lowers the crystallization temperature. The antifreeze compounds, a KCl and / or NaCl, and / or the hydrophilic polymer, copolymer, prepolymer or oligomer, characterized in that contained in the water, in claim 1 The method described.   3. A process according to claim 1 or 2, characterized in that the liquid does not freeze at a substrate temperature of high and -5 [deg.] C.   4. A method according to claim 3, characterized in that the liquid does not freeze at high substrate temperatures of -10 <0> C.   The process of Claims 1 to 4 characterized in that, prior to interposing a liquid between the film and the substrate, the substrate is removed of all particles attached to the substrate, cleaned and dried. The method as described in any one.   6. A method according to any one of the preceding claims, characterized in that the side of the flexible film that is adhered to the substrate is wetted with the liquid.   The method according to any one of claims 1 to 6, characterized in that the side of the flexible film that is bonded to the substrate comprises an adhesive layer.   The side of the flexible film that is bonded to the substrate includes an adhesive layer with a protective film that is removed prior to bonding to the substrate. The described method.   During the operation of applying the film to the substrate, the opposite side of the flexible film that is adhered to the substrate is wetted with the liquid so that a scraper can easily slide over the film. A method according to any one of the preceding claims, characterized in that   10. The surface of the soft film opposite to that bonded to the base material is provided with a protective film that is removed after the soft film is bonded to the base material. The method described in any one of the paragraphs.   The method according to any one of claims 1 to 10, wherein the liquid interposed between the film and the substrate contains one or more surfactants.   A substrate and a defrost soft film obtained by the method according to any one of claims 1 to 11 and forming a transparent assembly, the substrate and film being defrosted, Persistent absence of frost when transferred from an atmosphere having a temperature above 0 ° C. and a residual humidity of at least 25% to an atmosphere where the temperature of the substrate and the film will be below 0 ° C. A substrate and a flexible film, characterized in that   When the substrate and film are transferred from an atmosphere having a temperature above 0 ° C. and a residual humidity of at least 25% to an atmosphere where the temperature of the substrate and the film will be as high as −5 ° C. 13. A substrate and a flexible film according to claim 12, characterized in that frost is permanently absent.   When the substrate and film are transferred from an atmosphere having a temperature of 0 ° C. or higher and a residual humidity of at least 25% to an atmosphere where the temperature of the substrate and the film atmosphere will be as high as −10 ° C. The substrate and the flexible film according to claim 13, wherein frost is not continuously present.   The substrate and flexible film according to any one of claims 12 to 14, characterized in that the atmosphere is at a temperature between 10 and 35 ° C.   The substrate and flexible film according to any one of claims 12 to 14, characterized in that the atmosphere is at a temperature between 15 and 30 ° C.   The substrate and flexible film according to any one of claims 12 to 14, characterized in that the atmosphere is at a temperature between 23 and 27 ° C.   The film is hydrophobic and / or hydrophilic, and / or anti-fouling / (photocatalytic) self-cleaning, and / or reflects light or heat radiation, is sun protection, low Is radioactive and / or at least partially colored and / or electrically conductive / exothermic and / or semiconductive and / or antistatic and / or The substrate and the flexible film according to claim 12, wherein the substrate and the flexible film are electroluminescent. The film is, from a state at a temperature of higher -10 ° C., when moving in the atmosphere having 0 ℃ temperatures above and at least 25% residual moisture, characterized in that it does not produce at least 12 seconds frost, The base material and soft film as described in any one of Claims 12-18. The film is higher from the state at a temperature of -15 ° C., when moving in the atmosphere having a temperature and at least 25% residual moisture above 0 ° C., characterized in that it does not produce at least 12 seconds frost The base material and soft film as described in Claim 19. The film is higher from the state at a temperature of -20 ° C., when moving in the atmosphere having a temperature and at least 25% residual moisture above 0 ° C., characterized in that it does not produce at least 12 seconds frost The base material and soft film as described in Claim 20.   The substrate and the flexible film according to any one of claims 19 to 21, wherein the atmosphere has a temperature of 10 to 35 ° C.   The substrate and the flexible film according to any one of claims 19 to 21, wherein the air has a temperature of 15 to 30 ° C.   The substrate and the flexible film according to any one of claims 19 to 21, wherein the air has a temperature of 23 to 27 ° C.   A substrate and a flexible film according to any one of claims 19 to 24, characterized in that frost does not form for at least 1 minute.   26. A substrate and a flexible film according to claim 25, characterized in that frost does not form for at least 2 minutes.   27. A substrate and a flexible film according to claim 26, characterized in that frost does not form for at least 3 minutes.   The film is a polyolefin such as polyamide, polyester, polyethylene or polypropylene, cellulose, polystyrene, ethylene / vinyl acetate copolymer, polyvinyl alcohol, polyvinyl chloride, polyethylene terephthalate, polymethyl methacrylate, polycarbonate, polyvinyl butyral, polyurethane, polyvinyl pyrrolidone, Polyvinylpyridine, poly (2-hydroxyethyl acrylate) type polyacrylate, polyacrylamide, polyvinyl acetate, polyacrylonitrile, polyacrolein, polyethylene glycol, polyoxyethylene, or a copolymer or mixture of at least one of these polymers. Any one of 12 to 27, characterized in that it is based on a supported substrate. The described substrate and flexible film.   29. The substrate and flexible film according to any one of claims 12 to 28, wherein the film comprises an antifreeze compound that lowers the crystallization temperature. It includes beauty soft membrane Oyo to substrates according to any one of claims 12 to 29, and the substrate and the soft membrane is connected through the cavity filled with the intermediate adhesive layer or gas Glazing. It includes beauty soft membrane Oyo to substrates according to any one of claims 12 to 29, and the substrate and the soft membrane is connected through the cavity filled with the intermediate adhesive layer or gas Glazing also including other transparent sheets that have.   32. A glazing as claimed in claim 30 or 31 wherein the flexible film forms an outer surface.   The glazing according to any one of claims 30 to 32, wherein the barrier has a high thermal conductivity of 1.46 W / mK.   The use of glazing as claimed in any one of claims 30 to 33 as a door of a refrigerated cabinet.   A glazing application according to any one of claims 30 to 33 for elements of refrigerated cabinets other than buildings, street fixtures or poster panels, traffic mirrors and doors.   Use of glazing as claimed in any one of claims 30 to 33 for ground transport vehicles, airborne or water transport vehicles.   Use of glazing as claimed in any one of claims 30 to 33 for visual elements.